WO2021123922A1 - Intelligent compositions, packaging, and methods thereof - Google Patents
Intelligent compositions, packaging, and methods thereof Download PDFInfo
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- WO2021123922A1 WO2021123922A1 PCT/IB2020/020003 IB2020020003W WO2021123922A1 WO 2021123922 A1 WO2021123922 A1 WO 2021123922A1 IB 2020020003 W IB2020020003 W IB 2020020003W WO 2021123922 A1 WO2021123922 A1 WO 2021123922A1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/20—Compounding polymers with additives, e.g. colouring
- C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
- C08J3/226—Compounding polymers with additives, e.g. colouring using masterbatch techniques using a polymer as a carrier
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y70/00—Materials specially adapted for additive manufacturing
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y70/00—Materials specially adapted for additive manufacturing
- B33Y70/10—Composites of different types of material, e.g. mixtures of ceramics and polymers or mixtures of metals and biomaterials
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y80/00—Products made by additive manufacturing
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
- B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
- B65D65/00—Wrappers or flexible covers; Packaging materials of special type or form
- B65D65/38—Packaging materials of special type or form
- B65D65/40—Applications of laminates for particular packaging purposes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/10—Encapsulated ingredients
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/06—Polyethene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/08—Copolymers of ethene
- C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
- C08L23/0853—Vinylacetate
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y10/00—Processes of additive manufacturing
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/04—Homopolymers or copolymers of ethene
- C08J2323/06—Polyethene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2423/04—Homopolymers or copolymers of ethene
- C08J2423/08—Copolymers of ethene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/005—Additives being defined by their particle size in general
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/006—Additives being defined by their surface area
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
- C08K5/0041—Optical brightening agents, organic pigments
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N31/00—Investigating or analysing non-biological materials by the use of the chemical methods specified in the subgroup; Apparatus specially adapted for such methods
- G01N31/22—Investigating or analysing non-biological materials by the use of the chemical methods specified in the subgroup; Apparatus specially adapted for such methods using chemical indicators
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N31/00—Investigating or analysing non-biological materials by the use of the chemical methods specified in the subgroup; Apparatus specially adapted for such methods
- G01N31/22—Investigating or analysing non-biological materials by the use of the chemical methods specified in the subgroup; Apparatus specially adapted for such methods using chemical indicators
- G01N31/221—Investigating or analysing non-biological materials by the use of the chemical methods specified in the subgroup; Apparatus specially adapted for such methods using chemical indicators for investigating pH value
Definitions
- embodiments disclosed herein relate to an encapsulated indicator that includes a silica matrix encapsulating an acid-base indicator, wherein the acid-base indicator is present in its basic form.
- embodiments disclosed herein relate to an intelligent polymer composition that includes a polymer matrix; and an encapsulated indicator dispersed in the polymer matrix, wherein the encapsulated indicator includes a silica matrix encapsulating an acid-base indicator, wherein the acid-base indicator is present in its basic form.
- embodiments disclosed herein relate to an intelligent polymer composition that includes a matrix polymer and an encapsulated indicator, wherein the indicator triggers a color change in the intelligent polymeric composition when exposed to an external stimulus.
- embodiments disclosed herein relate to a packaging material that includes a packaging material formed from an intelligent polymer composition that includes a polymer matrix; and an encapsulated indicator dispersed in the polymer matrix, wherein the encapsulated indicator includes a silica matrix encapsulating an acid- base indicator, wherein the acid-base indicator is present in its basic form, and wherein the intelligent polymer composition is configured to contact a material enclosed within the packaging material
- embodiments disclosed herein relate to a packaging material that includes a packaging material formed from an intelligent polymer composition that includes a matrix polymer and an encapsulated indicator, wherein the indicator triggers a color change in the intelligent polymeric composition when exposed to an external stimulus, and wherein the intelligent polymer composition is configured to contact a material enclosed within the packaging material.
- embodiments disclosed herein relate to a method of forming encapsulated indicator that includes reacting at least one acid-base indicator with a non volatile alkaline compound to convert the acid-base indicator to its basic form; combining the acid-base indicator with a silica precursor; and precipitating the silica precursor to form a silica matrix encapsulating the acid-base indicator.
- embodiments disclosed herein relate to a method of forming an intelligent polymer composition that includes dispersing an encapsulated indicator in a polymer matrix to form the intelligent polymer composition that includes a polymer matrix; and an encapsulated indicator dispersed in the polymer matrix, wherein the encapsulated indicator includes a silica matrix encapsulating an acid-base indicator, wherein the acid-base indicator is present in its basic form.
- embodiments disclosed herein relate to a method of forming an intelligent polymer composition that includes dispersing an encapsulated indicator in a polymer matrix to form the intelligent polymer composition that includes a matrix polymer and an encapsulated indicator, wherein the indicator triggers a color change in the intelligent polymeric composition when exposed to an external stimulus.
- embodiments disclosed herein relate to method that includes forming a packaging material from an intelligent polymer composition that includes a polymer matrix; and an encapsulated indicator dispersed in the polymer matrix, wherein the encapsulated indicator includes a silica matrix encapsulating an acid-base indicator, wherein the acid-base indicator is present in its basic form.
- embodiments disclosed herein relate to method that includes forming a packaging material from an intelligent polymer composition that includes a matrix polymer and an encapsulated indicator, wherein the indicator triggers a color change in the intelligent polymeric composition when exposed to an external stimulus.
- embodiments disclosed herein relate to a method that includes manufacturing at least a first portion of an entire article using an additive manufacturing technique with an intelligent polymer composition, wherein the intelligent polymer composition comprises a matrix polymer and an indicator, wherein the indicator triggers a color change in the intelligent polymeric composition when exposed to an external stimulus.
- embodiments disclosed herein relate to a printed article that includes a plurality of printed layers, with at least a portion of the plurality of layers comprising an intelligent polymer composition, wherein the intelligent polymer composition comprises a matrix polymer and an indicator, wherein the indicator triggers a color change in the intelligent polymeric composition when exposed to an external stimulus.
- FIGS. 1A-B are schematics illustrating a bottle cap containing an intelligent polymer composition in accordance with embodiments of the present disclosure.
- FIGS. 2A-B are schematics illustrating packaging incorporating an intelligent polymer composition in accordance with embodiments of the present disclosure.
- FIGS. 3-6 are schematics illustrating various packaging configurations for incorporating an intelligent polymer composition in accordance with embodiments of the present disclosure.
- FIG. 7 shows ATR-FTIR spectrum of silica capsules according to embodiments of the present disclosure.
- FIGs. 8-14 shows an SEM image of silica capsules according to embodiments of the present disclosure.
- FIGs. 15-16 show color change progression for different molar ratios of indicator ro alkaline.
- FIG. 17 shows delta E over time for Examples 1-3 of the present disclosure.
- FIG. 18 shows delta E over time for Examples 2 and 3 of the present disclosure.
- FIG. 19 shows photographs of a 3D-printed bottle according to embodiments of the present disclosure.
- embodiments disclosed herein relate to encapsulated indicators that function as visual indicators in response to changes in the surrounding environment.
- indicators encapsulated in silica may be converted during synthesis of the silica capsules to the high end of the indicator’s pH scale.
- embodiments disclosed herein relate to intelligent polymer compositions that contain an indicator therein that responds to changes in the surrounding environment.
- intelligent polymer compositions including both neat (unmodified) or encapsulated indicators
- Intelligent polymer compositions in accordance with the present disclosure may optionally form all or at least a portion of a packaging material, including components that are made separately and combined with a second packaging material prepared by a separate process.
- intelligent polymer compositions may be formulated as a color-based pH indicator, such as for use in food packaging containing the color-based pH indicator, that is capable of detecting pH changes, such as in enclosed foods associated with various forms of microbe-induced spoilage, for example.
- intelligent polymer compositions may contain a polymer matrix prepared from a polymer or polymer mixture, and an indicator capable of detecting the pH of substances enclosed within a package constructed, at least in part, from the intelligent polymer composition and communicating by color change to an external observer.
- intelligent polymer compositions may include a pH indicator that detects pH changes in a range from 4 to 6, and may be constructed as a food container used to store milk and other dairy products.
- Indicators in accordance with the present disclosure may include indicators embedded within a suitable host material.
- matrix polymers in accordance with the present disclosure may be formulated to control the rate of diffusion of gases and liquids carrying triggering stimuli into the polymer matrix of the intelligent polymer composition.
- tuning the diffusion or permeability properties of a polymer composition may control the diffusion of external stimuli, such as acids, bases, and organics, into the polymer matrix to be detected by an indicator.
- diffusion of a polymer matrix may be modified to limit or eliminate leakage of the indictors into the surrounding environment.
- Intelligent polymer compositions in accordance with one or more embodiments of the present disclosure may include an encapsulated indicators embedded within an encapsulant matrix that may extend the useful life of intelligent polymer compositions in some applications, for example, by maintaining the concentration and brightness/apparent intensity of a color indicator.
- Indicators are often small molecules or molecular complexes, which may diffuse through pores created in a polymer network and escape into the surrounding media.
- an encapsulating matrix may be used to tune the sensitivity of an intelligent polymer composition by modifying the rate of diffusion of a chemical stimulus into the polymer matrix.
- the encapsulant matrix may also prevent degradation of indicators during polymer processing conditions, which may include elevated temperatures and shear stresses during processing techniques such as extrusion.
- Intelligent polymer compositions in accordance with the present disclosure may include (1) a matrix polymer, which may be a single polymer or blend of polymers; and (2) an intelligent additive, which may be encapsulated or non-encapsulated, depending on the application. That is, for example, in particular embodiments directed to intelligent polymer compositions used in additive manufacturing, it is envisioned that either encapsulated or non-encapsulated indicators may be used.
- polymer compositions may include a number of additives that modify physical properties of the polymer composition such as adjusting melt flow, hardness, pH detection range, and the like.
- intelligent polymer compositions in accordance with the present disclosure may be formulated to resist surface fouling by proteins and other hydrophobic compounds that may reduce detection sensitivity.
- the hydrophobicity of the matrix polymer in a composition may be modified to control the accumulation of proteins present in milk and other foodstuffs on a matrix polymer surface.
- the indicators hosted in silica capsules and polymeric formulations in which these capsules are dispersed can both be used as sensors for food, pharmaceutical, environmental, and analytical industries.
- Intelligent compositions in accordance with the present disclosure may include one or more converted indicators and non-converted indicators (optionally encapsulated, depending on the application) that are sensitive to external stimuli such as changes in pH, humidity, time, and the presence of acids and bases.
- the converted indicator When subjected to the appropriate stimuli, the converted indicator may exhibit visual changes, for example a color change, indicating that a change of a predetermined magnitude has occurred.
- the indicator may be a converted pH indicator and/or an indicator which changes color in the presence of an analyte, such as ammonia, sulfur derivatives, ethylene, amines, indole, escathol, acids (e.g., lactic acid, gluconic acid, or acetic acid) and combinations thereof. It is also envisioned that multiple indicators may be included in a polymer composition, where each indicator is sensitive to a different stimulus.
- an analyte such as ammonia, sulfur derivatives, ethylene, amines, indole, escathol, acids (e.g., lactic acid, gluconic acid, or acetic acid) and combinations thereof.
- acids e.g., lactic acid, gluconic acid, or acetic acid
- acid-base indicators may be one or more selected from Methyl Violet, Crystal Violet, Ethyl Violet, Malachite Green, 2-((p- (dimethylamino) phenyl) azo) pyridine, Quinaldine Red, para-methyl Red, Litmus, Metanil Yellow, 4-phenylazodiphenylamine, Thymol blue, m-Cresol Purple, Tropaeolin 00, 4-o-tolylazo-o-toluidine, Erythrosine sodium salt, Benzopurpurin 4B, N,N’-dimethyl- p-(m-tolylazo) Aniline, 2,4-Dinitrophenol, Methyl Yellow (N,N-Dimethyl-p- phenylazoaniline), 4,4'-bis(2-amino-l-naphthylazo)2,2'-stilbenedisulfonic acid, potassium salt of tetrabromophenolphthalein
- the terms “basic” and “basic form” of an indicator have the meaning that the indicator is in the form (“color”) of its transition that is on the higher end of its pH scale. For example, if a pH indicator has a low end transition at a pH value of 1 and a high end at a pH value of 3, when its color corresponds to the color for a pH value higher than 3, it has reached its higher end, and it is called “basic form”, even though the pH at which the high end transition occurs is an acidic pH. Similarly, for pH indicators having a low end transition that is at a basic pH, the basic form of the indicator is present when the indicator has transitioned to the higher end form, with a color corresponding to a pH value at the higher end transition.
- an indicator may be converted to an active form that reacts with a triggering stimulus, undergoing a color change.
- a pH indicator used to indicate the presence of an acid may be obtained in an acid form from a supplier or following synthesis and exhibit a color corresponding to an acid state.
- the indicator in order to have the indicator function to detect acid, the indicator may be converted (or charged) to the corresponding basic form and color by treatment with a strong base.
- an acidic material such as acetic acid or lactic acid produced by various microbes, initiates a color change for the material, providing a visual indicator of food spoilage.
- the acids compounds may neutralize the base used in the indicator conversion, and then as the acid continues to build up, the acid may react with the indicator, thereby changing its color.
- a bromothymol blue indicator may be converted with alkaline base to its characteristic blue color in high pH.
- generated acids may convert the indicator from blue to yellow, providing a visual indicator, for example, of food spoilage.
- concentration ratios between indicator and alkaline base may be used to convert the indicator, which may allow for control and modulation of the speed of the indicator’s color change depending on the concentration of the trigger (acid) that is generated.
- the present disclosure refers to the generation of acid during a food decomposition process
- the present disclosure is not so limited. Rather, it is understood that other process can release acidic compounds, and the embodiments of the present disclosure may be able to detect acidic vapors and solutions.
- the selected indicator for an intelligent polymer composition may be converted at any stage during the process of preparing the intelligent polymer composition, including prior to or after combination with the matrix polymer. Further, in one or more embodiments, the indicator may be converted prior, during, or after encapsulation, and prior to or after combination of the encapsulated indicator with the matrix polymer.
- the conversion of indicator may allow modulation of the response to stimuli over a period of time according to the concentration of the trigger generated in any process, such as aging and deterioration of different kinds of food. According to the nature and concentration of the base performing the conversion, the response rate (color change) of the indicator that is hosted in a capsule can be adjusted.
- indicators may be added to an intelligent polymer composition at a concentration having a lower limit selected from any of 10 ppm, 100 ppm, and 500 ppm, to an upper limit selected from any of 1,000 ppm, 5,000 ppm, 10,000 ppm, and 20,000 ppm, where any lower limit may be combined with any upper limit.
- a concentration having a lower limit selected from any of 10 ppm, 100 ppm, and 500 ppm to an upper limit selected from any of 1,000 ppm, 5,000 ppm, 10,000 ppm, and 20,000 ppm, where any lower limit may be combined with any upper limit.
- more or less indicator may be added depending on the particular application, and the conversion of the indicator can be modulated in accordance with the present disclosure.
- one or more indicators may be encapsulated prior to incorporation into an intelligent composition.
- Indicators in accordance with the present disclosure may optionally be encapsulated by an encapsulant that prevents the indicator from leaching into the surrounding polymer or environment, and/or protects the indicator from substantial degradation due to polymer processing conditions, but also allows diffusion of substances into the encapsulated indicator that trigger a color change.
- the encapsulant of the present disclosure by its intrinsic characteristics, may allow contact between an analyte and the indicator and, on the other hand, substantially inhibit the release of the indicator to the medium. In other words, the encapsulant protects the indicator, substantially avoiding or minimizing its leaching into the external environment.
- the encapsulant in which the indicator is encapsulated may be an organic, inorganic or hybrid matrix.
- indicators may be encapsulated by a matrix formed by the reaction of an encapsulant precursor such as silicon alkoxides or titanium alkoxides in some embodiments, or mixtures of silicone alkoxides and titanium alkoxides in other embodiments, which react to form a matrix that modifies the rate at which the indicator may leach into the surrounding polymer or environment and also protects the indicator from substantial degradation due to the polymer processing conditions.
- encapsulants may be prepared according to a sol-gel method, such as that described in U.S. Pat. No. 9,063,111, but not limited to the precursors described therein.
- alkoxide substituents of the encapsulant precursors may include Cl -Cl 2 alcohols, which may be linear or branched and may be substituted with various functional groups such as vinyl groups, alkyls, amines, amides, imines, carboxylates, and alcohols.
- a silica-based encapsulant may be modified to contain amine functionality by reaction with modified alkoxysilanes such as aminopropyltriethoxysilane (APTS).
- APTS aminopropyltriethoxysilane
- the indicator may be converted to an active form that reacts with a triggering stimulus, undergoing a color change, prior, during or after the encapsulation, forming an encapsulated converted indicator.
- the encapsulant is a modified encapsulant comprising functional groups that can convert the encapsulated indicator to an active form, forming an indicator converted by capsule chemistry.
- a pFl indicator used to indicate the presence of an acid may be obtained in an acid form from a supplier or following synthesis and exhibit a color corresponding to an acid state.
- the indicator may be encapsulated in an encapsulant comprising functional groups that stabilizes the corresponding basic form and color by the presence of basic functional groups in the encapsulant.
- a bromothymol blue indicator may be encapsulated in a silica-based encapsulant modified to contain amine functionality, converting the indicator to the corresponding basic form and characteristic blue color.
- an acidic material such as acetic acid or lactic acid produced by various microbes initiates a color change for the material from blue to yellow, providing a visual indicator of food spoilage.
- Embodiments of the present disclosure are also directed to methods of encapsulating the indicator in a matrix of silica through sol-gel routes.
- the sol-gel route may be via a basic catalysis, referred to as route (a), or a two-step basic/acidic catalysis, referred to as route (b).
- the encapsulation process of the indicator via basic catalysis sol-gel route comprises the following steps: i) Reacting the acid-base indicator or a mixture of acid- base indicators in their acid form with a non-volatile alkaline compound in an alcoholic medium; ii) Adding a volatile alkaline compound, such as ammonium hydroxide to the solution obtained in i); iii) Adding a tetralkylorthosilicate to the solution obtained in ii) to result in a chemical reaction of silica formation and the encapsulation of the indicator; iv) Removing the solvent of the product from the reaction obtained in iii); and optionally, v) Washing the product obtained in iv) with an alcohol and drying.
- a volatile alkaline compound such as ammonium hydroxide
- iii Adding a tetralkylorthosilicate to the solution obtained in ii) to result in a chemical reaction of silica formation and the encapsulation
- Step i) of the indicator encapsulation route (a) may involve reacting the acid-base indicator or a mixture of acid-base indicators in their acid form with an aqueous solution of a non-volatile alkaline compound in an alcoholic medium.
- the alkaline compound may be a strong base used to convert the indicator to its basic form.
- Representative but non-limiting examples of the acid-base indicator used in step i) of route (a) include: Methyl Violet, Crystal Violet, Ethyl Violet, Malachite Green, 2- ((p-(dimethylamino) phenyl) azo) pyridine, Quinaldine Red, para-methyl Red, Litmus, Metanil Yellow, 4-phenylazodiphenylamine, Thymol blue, m-Cresol Purple, Tropaeolin 00, 4-o-tolylazo-o-toluidine, Erythrosine sodium salt, Benzopurpurin 4B, N,N’- dimethyl-p-(m-tolylazo) Aniline, 2,4-Dinitrophenol, Methyl Yellow (N,N-Dimethyl-p- phenylazoaniline), 4,4'-bis(2-amino- l-naphthylazo)2,2'-stilbenedisulfonic acid, potassium salt of tetrab
- Representative, but non-limiting, examples of alcohols used in step i) of route (a) may include ethanol, 1 -propanol, 2-propanol, 1 -butanol, 2-butanol, 1-pentanol, 2- pentanol, 1-hexanol, 2 -hexanol, and mixtures thereof.
- non-volatile alkaline compounds used in step i) of route (a) may include alkaline metal bases such as lithium hydroxide, sodium hydroxide, potassium hydroxide, or organosilane bases such as aminopropyltriethoxysilane or aminopropyltrimethoxysilane, or mixtures thereof.
- alkaline metal bases such as lithium hydroxide, sodium hydroxide, potassium hydroxide, or organosilane bases such as aminopropyltriethoxysilane or aminopropyltrimethoxysilane, or mixtures thereof.
- the molar ratio of the indicator (or mixtures of indicators) to the alkaline compound may range from a lower limit or any of 1:20, 1:40, or 1:60, to an upper limit of any of 1:100, 1:150, or 1:200, where any lower limit can be used in combination with any upper limit.
- Step ii) of the indicator encapsulation route (a) may include adding a volatile alkaline compound, such as ammonium hydroxide to the solution obtained in i).
- a volatile alkaline compound such as ammonium hydroxide
- the molar concentration of a volatile alkaline compound in the alcohol solution used in step ii) of the indicator encapsulation route (a) may have a lower limit of any of 0.01, 0.1, 0.5, 1.0, or 2.0 mol /L to an upper limit of any of 7, 8, 9, or 10 mol /L, where any lower limit can be used in combination with any upper limit.
- Step iii) of the indicator encapsulation route (a) may include adding a tetraalkylorthosilicate to the solution obtained in ii), resulting in the chemical reaction of silica formation and in the encapsulation of the indicator.
- tetralkylorthosilicate compounds used in step iii) of route (a) may include tetramethylorthosilicate (TMOS), tetraethylorthosilicate (TEOS), tetrapropylortosilicate (TPOS), tetrabutylorthosilicate (TBOS) and / or a mixture thereof.
- TMOS tetramethylorthosilicate
- TEOS tetraethylorthosilicate
- TPOS tetrapropylortosilicate
- TBOS tetrabutylorthosilicate
- the ratio between the mass of indicator (g) and the volume (L) of tetralkylorthosilicate used in step iii) of route (a) may have a lower limit of any of 1, 2, 5, or 10 g/L and an upper limit of any of 20, 30, or 40 g/L, where any lower limit can be used in combination with any upper limit.
- the stirring speed used in step iii) of route (a) may be maintained between 50 and 5000 rpm.
- the reaction time of step iii) of route (a) may have a lower limit of any of 0.1, 0.2, or 0.3 h to an upper limit of any of 0.6, 2.0, 5.0, or 10 h.
- Step iv) of the indicator encapsulation route (a) may include removing solvent from the product from the reaction obtained in iii).
- Methods for solvent removal in step iv) of process (a) include but are not limited to: nitrogen flow drying, vacuum drying, evaporation, filtration and drying with supercritical fluid.
- Step v) of the indicator encapsulation route (a) may be optional and may include washing the product obtained in iv) with an alcohol and drying it.
- (a) are may include ethanol, 1 -propanol, 2-propanol, 1 -butanol, 2-butanol, 1-pentanol, 2-pentanol, 1-hexanol, 2 -hexanol, and mixtures thereof.
- the drying methods in step v) of route (a) may include but are not limited to: nitrogen flow drying, vacuum drying, evaporation, filtration and drying with supercritical fluid.
- the encapsulation process of the indicator via a two-step acid/basic catalysis sol- gel, also referred to as route (b) may include the following steps: i) Adding the acid- base indicator or mixture of acid-base indicators to an acidified alcoholic solution; ii) Adding and reacting a tetraalkylorthosilicate in the solution obtained in i); iii) Precipitating the silica containing the encapsulated indicator by adding a non-volatile alkaline compound to the solution obtained in ii); iv) Removing the solvent of the product from the reaction obtained in iii); v) Optionally, washing the product obtained in iv) with an alcohol and drying it; vi) Optionally, washing the product obtained in v) with an alkaline compound and drying it
- Step i) of the indicator encapsulation route (b) may include adding the acid-base indicator or a mixture of the acid-base indicators to an acidified alcoholic solution.
- Representative but non-limiting examples of the acid-base indicator used in step i) of route (b) include: Methyl Violet, Crystal Violet, Ethyl Violet, Malachite Green, 2- ((p-(dimethylamino) phenyl) azo) pyridine, Quinaldine Red, para-methyl Red, Litmus, Metanil Yellow, 4-phenylazodiphenylamine, Thymol blue, m-Cresol Purple, Tropaeolin 00, 4-o-tolylazo-o-toluidine, Erythrosine sodium salt, Benzopurpurin 4B, N,N’- dimethyl-p-(m-tolylazo) Aniline, 2,4-Dinitrophenol, Methyl Yellow (N,N-Dimethyl-p- phenylazoaniline), 4,4'-bis(2-amino- l-naphthylazo)2,2'-stilbenedisulfonic acid, potassium salt of tetrab
- Representative but non-limiting examples of alcohols used in step i) of route (b) may include ethanol, 1 -propanol, 2-propanol, 1 -butanol, 2-butanol, 1-pentanol, 2- pentanol, 1-hexanol, 2-hexanol, and mixtures thereof.
- acids which can be used to acidify the alcoholic solution in step i) of route (b) may include hydrochloric acid, nitric acid, sulfuric acid, acetic acid, oxalic acid and citric acid.
- the acidified alcoholic solution of step i) of route is acidified alcoholic solution of step i) of route
- (b) may have an acid concentration having a lower limit of any of 0.000001, 0.0001, 0.01, or 0.1 mol/L to an upper limit of any of 1, 2, or 3 mol/L.
- Step ii) of the indicator encapsulating route (b) may include adding and reacting a tetraalkylorthosilicate in the solution obtained in i).
- tetralkylorthosilicate compounds used in step (ii) of route (b) may include tetramethylorthosilicate (TMOS), tetraethylorthosilicate (TEOS), tetrapropylorthoosilicate (TPOS), tetrabutylorthosilicate (TBOS) and / or a mixture thereof.
- TMOS tetramethylorthosilicate
- TEOS tetraethylorthosilicate
- TPOS tetrapropylorthoosilicate
- TBOS tetrabutylorthosilicate
- the ratio between the mass of indicator (g) and the volume (L) of tetralkylorthosilicate used in step ii) of route (b) may have a lower limit of any of 1, 2, 5, or 10 g/L and an upper limit of any of 20, 30, or 40 g/L, where any lower limit can be used in combination with any upper limit.
- the reaction time of step ii) of route (b) may have a lower limit of any of 0.01, 0.1, 1, 2, or 4 hrs to an upper limit of any of 12, 24, 36, or 48 hrs.
- Step iii) of the indicator encapsulation route (b) may include precipitating the encapsulated indicator containing silica by adding an alkaline compound to the solution obtained in ii).
- alkaline compounds which may be volatile or non-volatile used in step iii) of route (b) are: alkaline metal bases such as lithium hydroxide, sodium hydroxide, potassium hydroxide, or ammonium hydroxide, or organosilane bases such as aminopropyltriethoxysilane or aminopropyltrimethoxysilane, or mixtures thereof.
- alkaline metal bases such as lithium hydroxide, sodium hydroxide, potassium hydroxide, or ammonium hydroxide
- organosilane bases such as aminopropyltriethoxysilane or aminopropyltrimethoxysilane, or mixtures thereof.
- the molar ratio of alkaline compound used in step iii) of route (b) and tetralkylorthosilicate may have a lower limit of any of 0.01:1.0, 0.1:1.0, 0.5:1.0, and 1.0:1.0 and an upper limit of any of 3.0:1.0, 4.0:1.0, or 5.0:1.0, where any lower limit can be used in combination with any upper limit.
- Step iv) of the indicator encapsulation route (b) may include removing the solvent from the reaction product obtained in iii).
- Methods for solvent removal in step iv) of route (b) include but are not limited to: nitrogen flow drying, vacuum drying, evaporation, filtration and drying with supercritical fluid.
- Step v) of the indicator encapsulation route (b) may be optional and may include washing the product obtained in iv) with an alcohol and drying it.
- Non-limiting examples of the alcohol used in step v) of route (b) may include ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 1-pentanol, 2-pentanol, 1- hexanol, 2-hexanol, and mixtures thereof.
- the drying methods in step v) of route (b) may include but are not limited to: nitrogen flow drying, vacuum drying, evaporation, filtration and drying with supercritical fluid.
- Step vi) of the indicator encapsulation route (b) may be optional and may include washing the product obtained in v) with an alkaline compound and drying it.
- alkaline compounds used in step vi) of route (b) may include lithium hydroxide, sodium hydroxide, potassium hydroxide, aminopropyltriethoxy silane, aminopropyltrimethoxysilane or mixtures thereof.
- the concentration of the alkaline compound used in step vi) of route (b) may have a lower limit of any of 0.01, 0.1, 0.5, 1.0, or 2.0 mol /L to an upper limit of any of 7, 8, 9, or 10 mol /L, where any lower limit can be used in combination with any upper limit.
- the alkaline compound used in step vi) of route (b) may be added in an equimolar amount relative to the tetralkylorthosilicate.
- the drying methods in step vi) of route (b) may include include but are not limited to: nitrogen flow drying, vacuum drying, evaporation, filtration and drying with supercritical fluid.
- the indicator may be added relative to the same weight of encapsulant precursor that may have a mole percent (mol%) that varies from 0.001 mol% to 10 mol% of indicator per mol of encapsulant precursor.
- Intelligent polymer compositions in accordance may contain a concentration of indicator at a percent by weight (wt%) of the polymer composition that may range from a lower limit selected from any of 0.005 wt%, 0.1 wt%, 1 wt% and 5 wt% to an upper limit selected from any of 10 wt%, 20 wt%, 30 wt% and 40 wt%, where any lower limit can be combined with any upper limit.
- wt% percent by weight
- One or more embodiments of the present disclosure may be directed to silica capsules, which may be prepared by routes (a) or (b), described above. These silica capsules contain an acid-base indicator converted by a non-volatile alkaline compound, wherein the molecules of that indicator are distributed both on the surface and in the bulk of the silica network forming the capsule. By virtue of the conversion, the silica capsules of the present disclosure may contain in its composition an alkaline compound from the conversion of the acid-base indicator to its basic form.
- the molar proportion between the acid-base indicator and the alkaline compound in the silica capsules of the present disclosure may have a lower limit of any of 1:20, 1:40, or 1:60 and an upper limit of any of 1:100, 1:150, or 1:200, where any lower limit can be used in combination with any upper limit.
- the amount of acid-base indicator encapsulated within the silica capsules of the present disclosure may have a lower limit of any of 1000, 2000, or 4000 ppm, and an upper limit of any of 30,000, 40,000, or 50,000 ppm, where any lower limit can be used in combination with any upper limit.
- the silica capsules of the present disclosure may have a spheroidal morphology with average particle size, measured by FEG-SEM, having a lower limit of any of 0.1, 0.5, or 1.0 micrometers, and an upper limit of any of 10, 20, or 50 micrometers, where any lower limit can be used in combination with any upper limit.
- the relative percentage of six-fold siloxane rings may be used in combination with any upper limit.
- (SiO) 6 to the total siloxane rings (considering (SiO)4 + (SiO) 6 ) measured by ATR- FTIR, in the silica capsules of the present disclosure may have a lower limit of any of 60, 70, or 80%, and an upper limit of any of 85, 90, 94, or 96 %.
- the specific surface area (SBET) of the silica capsules of the present disclosure may have a lower limit of any of 0.5, 1.0, or 10.0 m 2 /g and an upper limit of any of 100, 200, or 300 m 2 /g, where any lower limit can be used in combination with any upper limit.
- the average pore diameter (Pd BJH) of the silica capsules of the present disclosure may have a lower limit of any of 50, 100, or 150 A and an upper limit of any of 300, 400, or 500 A, where any lower limit can be used in combination with any upper limit.
- the BET constant of the silica capsules of the present disclosure may have a lower limit of any of 10, 25, or 50, and an upper limit of any of 300, 400, or 500, where any lower limit can be used in combination with any upper limit.
- Intelligent polymer compositions in accordance with the present disclosure may be prepared with a matrix polymer that forms a semi-permeable barrier between a packaged material and one or more embedded indicators (encapsulated in one or more embodiments, as described herein).
- Matrix polymers may include homopolymers, copolymers, heterophasic polymers and polymers blends.
- the matrix polymer may include polar polymers that may decrease leaching of an encapsulated indicator.
- the matrix polymer may include non-polar polymers. Further, in one or more embodiments, the matrix polymer may include both polar and non-polar polymers.
- the content of polar polymer in the matrix polymer composition may range from a lower limit of any of 0, 5, 10, 20 or 30 wt% to an upper limit of any of 40, 60, 80 or 100 wt% of the polymer composition.
- the polar polymer content in the matrix may vary depending on the application and its color change requirements (e.g. the presence of polar polymer may not be required when the application is for indication in highly concentrated medium).
- Matrix polymers in accordance with the present disclosure may include polyolefins, ethylene vinyl acetate (EVA), ethylene vinyl acetate rubber, polyamides, polyesters, poly acrylic acids, polymers of acrylonitrile, polymethylmethacrylate and derivatives, poly (vinyl acetate), cellulose acetate; polyethylene oxide, poly (vinyl butyl ether), phenolic resins, epoxy resins, polyacrylamides and copolymers of acrylamides, ethylene vinyl alcohol (EVOH), , polystyrenes, styrenic block copolymers such as styrene-ethylene/butylene-styrene (SEBS), terpolymers and mixtures thereof.
- Matrix polymers may include polymers generated from petroleum-based monomers and/or biobased monomers.
- Matrix polymer compositions in accordance with the present disclosure may include polyolefins.
- polyolefins include polymers produced from unsaturated monomers (olefins or “alkenes”) with the general chemical formula of C n tb n -
- polyolefins may include ethylene homopolymers, copolymers of ethylene and one or more C3-C20 alpha-olefins, propylene homopolymers, heterophasic propylene polymers, copolymers of propylene and one or more comonomers selected from ethylene and C4-C20 alpha-olefins, olefin terpolymers and higher order polymers, and blends obtained from the mixture of one or more of these polymers and/or copolymers.
- polyolefins may be generated with a suitable catalyst such as Ziegler-Natta, metallocene, post-metalloc
- polyolefins are selected from polyethylene, polypropylene and combinations thereof.
- polyethylenes may include polyethylenes having a monomodal, bimodal, trimodal or multimodal molecular weight distribution.
- Polyolefins may be monomodal or multimodal compositions.
- “modality” of a polymer may refer to the shape of a molecular weight distribution for a population of polymer molecules in a polymer sample. The rate of chain propagation in a polymerization is not uniform and, as a result, distributions of molecular weights will exist in a polymer sample obtained from a reactor.
- the different polymer fractions will have distinct molecular weight distributions, which will be present as multiple maxima or a broadened peak.
- “multimodal” refers to a polyolefin composition exhibiting two or more distinct peaks within the molecular weight distribution.
- multimodal polyolefin compositions may include a low molecular weight (LMW) fraction and a high molecular weight (HMW) fraction.
- LMW low molecular weight
- HMW high molecular weight
- the ratio of the LMW fraction and the HMW fraction may range from a lower limit selected from any of 20:80, 40:60, and 50:50, to an upper limit selected from any of 55:45, 60:40, and 80:20, where any lower limit can be combined with any upper limit.
- polyolefins include polyethylene, including ethylene homopolymer and/or ethylene copolymers with one or more C3-C20 alpha- olefins, and combinations thereof.
- polyethylene may include polyethylene generated from petroleum based monomers and/or biobased monomers, such as ethylene obtained by the dehydration of biobased alcohols obtained from sugarcane.
- biobased polyethylenes are the “I’m Green”TM line of bio-polyethylenes from Braskem S.A.
- Ethylene Vinyl Acetate Copolymer (EVA)
- Matrix polymer compositions in accordance with the present disclosure may include EVA copolymers.
- EVA copolymers are prepared by the copolymerization of ethylene and vinyl acetate.
- the EVA copolymer can be derived from fossil or renewable sources such as biobased EVA.
- Biobased EVA is an EVA wherein at least one of ethylene and/or vinyl acetate monomers are derived from renewable sources, such as ethylene derived from biobased ethanol.
- the vinyl acetate content of the EVA copolymer may range from a lower limit of any of 8, 10, 12, 16, or 20, to an upper limit of any of 20, 40, 60, or 80%wt, where any lower limit can be used in combination with any upper limit.
- the EVA copolymer may have a melt flow index (MFI), measured according to ASTM D1238 with a load of 2.16 kg at 190°C, may have a lower limit of any of 0.1, 0.5, 1.0, 2.0, or 5.0 g/10 min and an upper limit of any of 25, 50, 75, 100, 125, or 150 g/10 min.
- MFI melt flow index
- Polymer compositions in accordance to the present disclosure may include an ethylene vinyl acetate (EVA) rubber resin prepared from of (A) EVA copolymer, (B) ethylene alpha-olefin copolymer, (C) polyorganosiloxane, (D) plasticizer, and (E) rubber.
- EVA rubber composition may include components generated from petroleum based monomers and/or biobased monomers, including the EVA copolymer and the ethylene alpha-olefin copolymer.
- EVA rubber compositions are prepared as disclosed in the Brazilian patent BR102012025160-4 and US2019/0315949, both of which are incorporated herein by reference in their entirety.
- EVA rubber resins may be selected from commercially available resins by Braskem such as VA4018R, VA1518A, VA8010SUV, SVT2145R, and combinations thereof.
- EVA rubber compositions in accordance may incorporate one or more EVA copolymers prepared by the copolymerization of ethylene and vinyl acetate.
- the EVA copolymer can be derived from fossil or renewable sources such as biobased EVA.
- Biobased EVA is an EVA wherein at least one of ethylene and/or vinyl acetate monomers are derived from renewable sources, such as ethylene derived from biobased ethanol. It is envisioned that the EVA copolymer present in the EVA rubber composition may include those discussed above.
- EVA rubber compositions in accordance with the present disclosure may contain an ethylene vinyl acetate copolymer at a percent by weight (wt%) of the composition that ranges from a lower limit of 20 wt%, 30 wt%, 40 wt%, or 50 wt%, to an upper limit of 60 wt%, 70 wt%, 80 wt%, or 90 wt%, where any lower limit may be paired with any upper limit.
- wt% percent by weight
- EVA rubber compositions in accordance may incorporate one or more copolymers prepared from the polymerization of ethylene and a C3 to C20 alpha-olefin.
- EVA rubber compositions in accordance with the present disclosure may contain an ethylene alpha-olefin copolymer at a percent by weight (wt%) of the composition that ranges from a lower limit of 5 wt% or 10 wt%, to an upper limit of 30 wt% or 60 wt%, where any lower limit may be paired with any upper limit.
- EVA rubber compositions in accordance may incorporate a polyorganosiloxane.
- suitable polyorganosiloxanes include a linear chain, branched, or three-dimensional structure, wherein the side groups can include one or more of methyl, ethyl, propyl groups, vinyl, phenyl, hydrogen, amino, epoxy, or halogen substituents.
- the terminal groups of the polyorganosiloxane may include hydroxyl groups, alkoxy groups, trimethylsilyl, dimethyldiphenylsilyl, and the like.
- Polyorganosiloxanes in accordance with the present disclosure may include one or more of dimethylpolysiloxane, methylpolysiloxane, and the like.
- EVA rubber compositions in accordance with the present disclosure may contain a polyorganosiloxane at a percent by weight (wt%) of the composition that ranges from a lower limit of 0.1 wt% or 0.5 wt%, to an upper limit of 5 wt% or 10 wt%, where any lower limit may be paired with any upper limit.
- wt% percent by weight
- EVA rubber compositions in accordance may incorporate a plasticizer to improve the processability and adjust the hardness of the EVA rubber.
- Plasticizers in accordance with the present disclosure may include one or more of bis(2-ethylhexyl) phthalate (DEHP), di-isononyl phthalate (DINP), bis (n-butyl) phthalate (DNBP), butyl benzyl phthalate (BZP), di-isodecyl phthalate (DIDP), di-n-octyl phthalate (DOP or DNOP), di- o-octyl phthalate (DIOP), diethyl phthalate (DEP), di-isobutyl phthalate (DIBP), di-n- hexyl phthalate, tri-methyl trimellitate (TMTM), tri-(2-ethylhexyl) trimellitate (TEHTM- MG), tri-(n-octyl, n-
- EVA rubber compositions in accordance with the present disclosure may contain a plasticizer at a percent by weight (wt%) of the composition that ranges from a lower limit of 0.5 wt% or 2 wt%, to an upper limit of 10 wt% or 20 wt%, where any lower limit may be paired with any upper limit.
- wt% percent by weight
- EVA rubber compositions in accordance may incorporate a rubber component to increase the rubbery touch and increase the coefficient of friction, depending on the end application.
- Rubbers in accordance with the present disclosure may include one or more of natural rubber, poly-isoprene (IR), styrene and butadiene rubber (SBR), polybutadiene, nitrile rubber (NBR); polyolefin rubbers such as ethylene-propylene rubbers (EPDM, EPM), and the like, acrylic rubbers, halogen rubbers such as halogenated butyl rubbers including brominated butyl rubber and chlorinated butyl rubber, brominated isotubylene, polychloroprene, and the like; silicone rubbers such as methylvinyl silicone rubber, dimethyl silicone rubber, and the like, sulfur-containing rubbers such as polysulfidic rubber; fluorinated rubbers; thermoplastic rubbers such as elastomers based on styrene, butadiene, isopre
- EVA rubber compositions in accordance with the present disclosure may contain a rubber at a percent by weight (wt%) of the composition that ranges from a lower limit of 0.5 wt% or 1 wt%, to an upper limit of 20 wt% or 40 wt%, where any lower limit may be paired with any upper limit.
- wt% percent by weight
- intelligent polymer compositions may include a matrix stabilizer that modifies the acidity/alkalinity of the system (matrix and indicator), preventing reversion of the indicator following a color change upon reaction with stimuli resulting from processing byproducts (e.g. acetic acid from EVA).
- matrix stabilizers may include stearate salts such as sodium stearate and calcium stearate, magnesium oxide, calcium carbonate, talc, and the like.
- an acidity/alkalinity modifier may be added to an intelligent polymer composition at a concentration having a lower limit selected from any of 100 ppm, 300 ppm, and 600 ppm, to an upper limit selected from any of 9,500 ppm, 10,000 ppm, and 20,000 ppm, where any lower limit may be combined with any upper limit.
- Intelligent polymer compositions in accordance with the present disclosure may incoporate one or more functional additives, including stabilizers such as distearyl pentaerythritol phosphite; metal compounds such as zinc 2-ethylhexanoate; epoxy compounds such as epoxidized soybean oil and epoxidized linseed oil; nitrogen compounds such as melamine; phosphorus compounds such as tris(nonylphenyl)phosphite; UV absorbers such as Hindered Amine Light Stabilizer compounds, benzophenone compounds and benzotriazole compounds; antioxidants; silicone oils; fillers such as clay, kaolin, talc, hydrotalcite, mica, zeolite, perlite, diatomaceous earth, calcium carbonate, glass (beads or fibers), and wood flour; foaming agents; foaming aids; crosslinking agents; crosslinking accelerators; flame retardants; dispersants; and processing aids such as resin additives.
- functional additives including stabilizer
- additives may include plasticizers, acid scavengers, stearates, antimicrobials, antioxidants, flame retardants, light stabilizers, antistatic agents, colorants, pigments, perfumes, chlorine scavengers, and the like.
- Intelligent polymer compositions in accordance with the present disclosure may be prepared by extrusion using standard processing parameters for polyolefins, such as temperature profile and screw profile (for example, twin-screw, with the use of distributive and dispersive mixing elements).
- standard processing parameters for polyolefins such as temperature profile and screw profile (for example, twin-screw, with the use of distributive and dispersive mixing elements).
- batch mixers such as mixing chambers, banbury mixers, and the like, using standard processing conditions and temperature profile for polyolefins may be used.
- one or more subsequent steps may be used in order to produce the actual part, using the same equipment and very similar processing parameters (e.g. extrusion blow molding (EBM), injection stretching blow molding (ISBM), injection molding, thermoforming, film extrusion, blown film extrusion, sheet extrusion, additive manufacturing, and the like).
- EBM extrusion blow molding
- ISBM injection stretching blow molding
- thermoforming thermoforming
- film extrusion blown film extru
- polymer components may be combined in a single step or as a series of combination steps.
- a subset of intelligent polymer composition components may be combined concurrently or separately in an extruder as a masterbatch or a final composition. It is also envisioned, for example, that most components of the formulation may be added together, with the polymeric matrix subsequently being added.
- polymer compositions in accordance with the present disclosure may be formulated as a “masterbatch” in which the polymer composition contains concentrations of indicator that are high relative to the indicator concentration in a final polymer blend for manufacture or use.
- a masterbatch stock may be formulated for storage or transport and, when desired, be combined with additional polyolefin or other matrix polymers in order to produce a final polymer composition having concentration of constituent components that provides indicator, physical, and chemical properties tailored to a selected end-use.
- a masterbatch can be made with the indicator and one or more additives in a first matrix polymer compound, which is subsequently diluted afterwards in a second matrix polymer, which may be the same or different matrix polymer.
- the masterbatch may be formulated and then diluted so that the final formulation possesses adequate concentration of indicator and one or more additives.
- a masterbatch polymer composition may contain a percent by weight of the total composition (wt%) of indicator (which may, for example, be an encapsulated indicator, i.e., capsules) s ranging from a lower limit selected from one of 5, 7, 9 or 10wt% to an upper limit selected from one of 15, 18 or 20 wt%, where any lower limit can be used with any upper limit.
- a masterbatch may include a matrix polymer (preferably, polar polymer) in an amount that ranges from a lower limit selected from 80, 82, or 85 wt% to an upper limit selected from one of 90, 91, 93 or 95 wt%, where any lower limit can be used with any upper limit.
- the polymer composition contains concentrations of indicator that are high relative to the indicator concentration in a final polymer blend for manufacture or use.
- the masterbatch composition may be combined with an additional quantity of matrix polymer to arrive at a indicator concentration in the final composition that is lower than the masterbatch concentration.
- the lower quantities of indicator and higher quantities of matrix polymer may be used, to arrive at the concentrations described above.
- intelligent polymer compositions of the present disclosure may be processed via extrusion.
- processing via twin screw extruder may have good dispersion and distribution capabilities (to disperse the indicator into the polymer matrix) to provide a homogeneous and time -phased color change.
- set temperature, screw profile, throughput rate, screw rotation, and residence time may be selected.
- polar blend components e.g., EVA
- a melt temperature below 210°C, preferentially below 200°C may be selected to minimize or reduce thermal degradation and release of acid compounds that might interact with the indicator.
- screw speeds may be controlled in order to avoid excessive heat generated by shear.
- An example of a temperature profile range for an HDPE and EVA blend in an intelligent composition is as shown in Table 2, where the lower part of the range would be more adequate for a higher MFR matrix.
- Example processing conditions for a lab scale TSE may include: a throughput rate of 2-4 kg/h, screw speed 200 - 280 rpm, with a relatively high- shear screw profile, where the residence time would be in the range from 25 to 90 s.
- an extrusion may use a Coperion ZSK-18 extruder.
- melt temperatures may be below 200°C. Therefore, screw speed, which controls throughput rate of a certain machine, and also its profile and shear level, may be considered for each specific system (extruder + blowing unit), in order to avoid thermomechanical degradation of the blend polar component (e.g., EVA).
- EBM Extrusion Blow Molding
- Table 3 An example of blow molding parameters to an industrial EBM (Extrusion Blow Molding) machine TECHNE-5000, for small volume parts is shown in Table 3:
- Intelligent polymer compositions may be adapted for use in a number of polymer processes including extrusion, coextrusion, extrusion coating, extrusion lamination, blown film extrusion, cast film extrusion, injection molding, blow molding, injection- blow molding, rotomolding, pultrusion, compression molding, solution casting, thermoforming, and additive manufacturing.
- One or more embodiments disclosed herein relate to packaging produced by various additive manufacturing (AM) techniques that incorporate intelligent polymer compositions capable of providing visual indicators of product quality in response to changes in packaged goods.
- Polymer compositions in accordance with the present disclosure may be used to generate 3D printed intelligent packaging containing color- based pH indicators capable of detecting pH changes in enclosed materials and foods associated with various forms of microbe-induced spoilage.
- embodiments of packaging produced by additive manufacturing may include use of either or both of unencapsulated and encapsulated indicators.
- the indicator (whether or not it is encapsulated) may be incorporated into an intelligent polymer composition, including the intelligent polymer compositions discussed above, for use in forming, for example, a packaging material manufactured by additive manufacturing.
- packaging materials such as caps, lids, bottles, boxes, and the like, may be generated from intelligent polymer compositions.
- packaging materials having components that include both standard polymers and intelligent polymer compositions may be constructed in a single manufacturing step.
- intelligent polymer composition may be integrated into a 3D printing process to generate articles having a fraction of the structure that is intelligent, while the remainder of the article may be selected for structural and/or aesthetic properties.
- AM techniques may be used to produce simple packaging with intelligent functionality, while minimizing the costs of specialized materials and obviating the need for additional steps to install labels or sensing devices.
- AM techniques in accordance with the present disclosure may include extrusion- based techniques such as fused deposition modeling (FDM) or freeforming, electro photography (EP), jetting, selective heat sintering (SHS), selective laser melting (SLM), selective laser sintering (SLS), high speed sintering (HSS), selective absorbing sintering (SAS), selective inhibition sintering (SIS), powder/binder jetting, electron-beam melting, and stereolithographic processes.
- FDM fused deposition modeling
- EP electro photography
- SHS selective heat sintering
- SLM selective laser melting
- SLS selective laser sintering
- HSS high speed sintering
- SAS selective absorbing sintering
- SIS selective inhibition sintering
- Intelligent polymer compositions may be adapted for use in various additive manufacturing processes.
- Additive manufacturing systems in accordance with the present disclosure include any system that prints, builds, or otherwise produces 3D parts and/or support structures.
- Additive manufacturing systems may be a stand-alone unit, a sub-unit of a larger system or production line, and/or may include other non-additive manufacturing features, such as subtractive-manufacturing features, pick-and-place features, two-dimensional printing features, and the like.
- additive manufacturing techniques may include material extrusion, material jetting, binder jetting, material jetting, vat photopolymerization, sheet lamination, powder bed fusion and directed energy deposition.
- the most widely used of these AM technologies is based on material extrusion.
- examples of commercially available additive manufacturing techniques include extrusion-based techniques such as fused deposition modeling (FDM) or freeforming, electro-photography (EP), jetting, selective heat sintering (SHS), selective laser melting (SLM), selective laser sintering (SLS), high speed sintering (HSS), selective absorbing sintering (SAS), selective inhibition sintering (SIS), powder/binder jetting, electron-beam melting, and stereolithographic processes.
- FDM fused deposition modeling
- EP electro-photography
- SHS selective heat sintering
- SLM selective laser melting
- SLS selective laser sintering
- HSS high speed sintering
- SAS selective absorbing sintering
- SIS selective inhibition sinter
- the digital representation of the 3D part is initially sliced into multiple horizontal layers. For each sliced layer, a tool path is then generated, which provides instructions for the particular additive manufacturing system to print the given layer.
- Particular additive manufacturing techniques that may be particularly suitable for the present polymer compositions include, for example, fused deposition modeling, selective laser sintering, high speed sintering, material jetting, or plastic freeforming.
- a 3D part may be printed from a digital representation of the 3D part in a layer-by-layer manner by extruding a flowable part material.
- the part material is extruded through an extrusion tip carried by a print head of the system, and is deposited as a sequence of roads on a substrate in an x-y plane.
- the extruded part material fuses to previously deposited part material, and solidifies upon a drop in temperature.
- the position of the print head relative to the substrate is then incremented along a z-axis (perpendicular to the x-y plane), and the process is then repeated to form a 3D part resembling the digital representation.
- a filament or granules formed from an intelligent polymer composition discussed above are heated and extruded through an extrusion head that deposits the molten plastic in X and Y coordinates, while the build table lowers the object layer by layer in the Z direction.
- Plastic freeforming such as that offered by ARBURG GmbH and Co KG (Lossburg, Germany), operates using standard granulated plastics that are melted such as in an injection molding process.
- a clocked nozzle that opens and closes (up to 100 times a second) builds the component layer-by-layer from miniscule plastic droplets. Further description about such technique may be found in U.S. Patent No. 9,039,953, which is herein incorporated by reference in its entirety.
- Selective laser sintering uses powdered material in the build area instead of liquid or molten resin.
- a laser is used to selectively sinter a layer of granules, which binds the material together to create a solid structure. When the object is fully formed, it’s left to cool in the machine before being removed.
- HSS high speed sintering
- manufacturing occurs by depositing a fine layer of polymeric powder, after which inkjet printheads deposit an infrared (IR) absorbing fluid (or toner powder) directly onto the powder surface where sintering is desired.
- IR infrared
- SLS and HSS are detailed as examples of powder bed fusion techniques, it is also envisioned that the intelligent polymer compositions may be adapted for use in other powder bed fusion techniques such as selective heat sintering (SHS), selective laser melting (SLM), selective absorbing sintering (SAS), and selective inhibition sintering (SIS).
- SHS selective heat sintering
- SLM selective laser melting
- SAS selective absorbing sintering
- SIS selective inhibition sintering
- Intelligent polymer compositions may be used in a number of fields as a visual indicator of changes such as pH temperature, humidity, time, and the presence of organic volatiles and/or oxygen.
- intelligent polymer compositions may be applied in various forms of food packaging and packaging elements such as windows inserts, films, and the like, to communicate particular qualities of the food through color change in response to stimuli.
- intelligent compositions may undergo a color change in response to pH changes induced by spoilage organisms, which indicates to a consumer the presence of food degradation.
- a cap 102 for a bottle or other container is constructed from a polymer and includes an intelligent polymer composition insert 104 formed by an intelligent polymer composition.
- an indicator embedded in the intelligent polymer compositions 104 detects a change in pH or other appropriate stimuli for materials contained within the bottle, the insert 106 changes color to convey this information to a consumer as shown in FIG. IB.
- the intelligent composition may be in direct contact with an enclosed material, contact may be temporary through splashing, or contact may be indirect through vapors generated from a solid or liquid material.
- FIG. 2A a bag constructed from an intelligent polymer composition 202 is shown having a reservoir for storing a material 204, such as a liquid or solid.
- a material 204 such as a liquid or solid.
- the packaging will undergo a visible change in color that alerts the consumer as to the change in material quality.
- the intelligent polymer composition may change in color entirely when the indicator is triggered, or the color change may be limited to the portion of the packaging contacting the material.
- FIG. 2B a design for a bottle constructed from an intelligent polymer composition 206 is shown having a reservoir for storing a material 204, such as a liquid or solid.
- a material 204 such as a liquid or solid.
- a bottle 302 is constructed having an indicator window 304 constructed from an intelligent polymer composition.
- the window 304 may be clear or translucent, and may be used to visualize the level of a liquid or solid 306 contained within the bottle 302, in addition to functioning as a visual indicator of material quality.
- the packaging will undergo a visible change in color that alerts the consumer as to the change in material quality.
- a bottle 402 constructed from a polymer is shown containing an intelligent polymer composition insert 404 formed by an intelligent polymer composition.
- an indicator embedded in the intelligent polymer compositions 104 detects a change in pH or other appropriate stimuli for materials contained within the bottle, the insert 106 changes color to convey this information to a consumer.
- the insert may have an extended well 406 that contacts a fluid or solid within a reservoir within the bottle 402. The well 406 may be used in cases where contact with a material is desired as the material within the bottle 402 is depleted through use.
- a bottle 502 constructed from a polymer is shown containing an intelligent polymer composition insert 506 formed by an intelligent polymer composition.
- the insert 506 changes color to convey this information to a consumer.
- the insert 506 is present on the underside of the package and contacts a material within a reservoir in bottle 502, allowing a consumer to verify the material quality by the status of the indicator in the insert 506 by inverting the package, despite the level of the material changing as it is used.
- the bottom 504 of the bottle 502 may be shaped to direct materials to insert 506 to increase sensitivity of the insert as the level of material in the bottle 502 is depleted.
- gray shading or text indicates regions of the article printed with an intelligent polymer composition that may include one or more indicators responsive to various stimuli.
- intelligent polymer compositions in accordance with the present disclosure may be used in part or in whole of rigid and flexible containers, films, multilayer films, sheets, bottles, cups, containers, pouches, caps, labels, intelligent coatings, among others, as well as molded articles such as pipes, tanks, drums, water tanks, household appliances, packaging for healthcare products and medical devices, automotive applications, agrochemical applications, silo bags, smart windows, product labeling, geomembranes, housewares, mulching, and personal protective gear such as air filters and gas masks. Intelligent polymer compositions may also be used in leak detecting devices, such as those installed on gas and liquid pipelines.
- intelligent polymer compositions in accordance with the present disclosure may be used in blow molded bottles for food spoilage detection, such as bottles to detect liquid food, such as milk, spoilage detection.
- the intelligent polymer compositions in accordance with the present disclosure may be applied in multilayer packaging, such as multilayer bottles or containers.
- multilayer packaging such as multilayer bottles or containers.
- the innermost layer in contact with the food may be formed by the intelligent polymer compositions in accordance with the present disclosure and the one or more outermost layers may be formed by other materials that have a transparency sufficient to allow the detection of color change.
- Intelligent polymer compositions in accordance with the present disclosure incorporate one or more indicators that respond to a predetermined reactive stimulus that initiates a color change in the polymer material that may be observable by eye and/or ultraviolet- visible spectrophotometer. While particular systems are described below with respect to the quantification of color change of intelligent polymer compositions, it is envisioned that any system capable of registering the change in color of an indicator or polymer composition containing an indicator may be used.
- the total color difference (TCD) exhibited by an indicator may be quantified by a TCD index such as a CieLAB color change index (DE) that uses L*, a*, b* values to describe the color of the polymer.
- DE is the difference in the color of the polymer before and after the contact with the external stimuli, and may be calculated in some embodiments according to Eq. (1) as described in Francis, F.J. 1983, Colorimetry of food, Peleg M. and Bagley E.B. (Eds.). Physical Properties of Foods, p. 105-123.Westport: AVI Publishing.
- L* refers to luminosity and a* and b*, are the chromatic coordinates.
- the parameter a varies from green (negative values) to red (positive values).
- the parameter b varies from blue (negative values) to yellow (positive values).
- Francis (1983) reported that TCD more than 5.0 could be easily detected by unaided eyes and TCD more than 12 presented a clearly different shade of color. The determination of DE values are known throughout the literature, and measurement systems such as the CieLAB color system are commercially available.
- intelligent polymer compositions in accordance with the present disclosure may exhibit a color change that is detectable by eye after exposure to the external stimuli, which corresponds to a DE of at least 8 or more. In some embodiments, intelligent polymer compositions in accordance with the present disclosure may exhibit a color change corresponding to a DE of at least 12 following exposure to the external stimuli.
- the X-rite Colorimeter is used for colorimetric analysis of samples provides data based on the CIELab color space.
- the CIELab is a spherical system representative of color composed of three different axes: L* for the lightness from black (0) to white (100), a* from green (-) to red (+), and b* from blue (-) to yellow (+). Each color is represented by a point (L*, a*, b*) internal to the sphere.
- the colorimeter captures the color of the object and provides its numerical representation in the system CIELab.
- FEG-SEM image of silica capsules and distribution of these silica capsules in the polymer composition were obtained using an FEG INSPECT F50 SEM from FEI company with 5 keV.
- the samples were metalized with gold or carbon using a Leica EM SCD500.
- FT-IR measurements were carried out using a Shimadzu spectrophotometer (IR Prestige 21), combining 32 scans at a 2 cm 1 resolution. Samples were directly analyzed in absorbance mode using attenuated total reflectance infrared spectroscopy (Gladi-ATR- Pike Technologies).
- Silica-based materials have a long-range amorphous structure, which results from a random network of elementary S1O4 units, locally arranged into cyclosiloxanes, containing mostly four and six Si atoms.
- the relative proportions of these cyclic units can be obtained from the deconvolution of the v as (Si-0)Si-0-Si infrared band.
- the four components were previously assigned to the longitudinal and transverse optical doublets (LO/TO) in four-fold, (SiO)4, and six-fold, (SiO)6, siloxane rings in according with the literature (A. Fidalgo, R. Ciriminna, L. M. Ilharco, M. Pagliaro. Chem. Mater. 17 (2005) 66-86).
- An estimation of the percentage of (SiO) 6 can be obtained for each sample from the following ratio: (areas of LC> 6 + TO, components)/(total area of V as (Si-O) band).
- N2 adsorption isotherms were performed on a Micromeritics Gemini 2375. The samples were pre -heated to 80 °C for 24 hours under a vacuum. The surface area (SBET) and the BET constant (C), a measure of the interaction force between the adsorbate (nitrogen) molecules and the adsorbent, were determined using the Brunauer-Emmett- Teller (BET) method at 77.4 K in the range 0.01 ⁇ P/P atm ⁇ 0.35. The average diameter of the pores was calculated using the Barrett-Joyner-Halenda (BJH) standards and the method proposed by Halsey for consideration of the desorption isotherm.
- BJH Barrett-Joyner-Halenda
- the pore volume was calculated using the /-plot and the isotherm pattern of Harkins and Jura (present in LOWELL, S., et al. Characterization of Porous Solids and Powders: Surface Area, Pore Size and Density. Kluwer Academic Publishers, 2004).
- Capsule A Characterization of the Capsule A is provided in Table 4:
- Capsule B Characterization of the Capsule B is provided in Table 5:
- Examples 1, 2, and 3 were formulated with 50 wt% of EVA HM728, -49.5 wt% of HDPE HD7000C, 0.5 wt% of Capsules A, B, and C (respectively), and 500 ppm of calcium stearate (matrix stabilizer), which were processed via mixing chamber using rolling-rotors, with a rotor speed of 100 rpm, set temperature of 180°C, and a mixing time of 2 minutes. After compression molding ( ⁇ 30 seconds, - 1 bar), the polymeric mass was taken directly from the mixing chamber into a thin plate (1mm).
- Example 4 Formulation and processing of the materials - plate
- Example 4 was formulated with 15 wt% of EVA HM728, -84.5 wt% of HDPE HD7000C, 0.5%wt of Capsule B, and 500 ppm of calcium stearate (matrix stabilizer), which was processed via mixing chamber using rolling-rotors, with a rotor speed of 100 rpm, set temperature of 180°C, and a mixing time of 2 minutes. After compression molding (- 30 seconds, - 1 bar), the polymeric mass was taken directly from the mixing chamber into a thin plate (1mm).
- Example 5 Formulation and processing of the materials - plate
- Example 5 was formulated with 35 wt% of EVA HM728, -64.5 wt% of HDPE HD7000C, 0.5 wt% of Capsules B, and 500 ppm of calcium stearate (matrix stabilizer), which was processed via mixing chamber using rolling-rotors, with a rotor speed of 100 rpm, set temperature of 180°C, and a mixing time of 2 minutes. After compression molding ( ⁇ 30 seconds, ⁇ 1 bar), the polymeric mass was taken directly from the mixing chamber into a thin plate (1mm).
- Examples 6, 7, and 8 were formulated with 50 wt% of EVA HM728, -49.5 wt% of HDPE HD7000C, 0.5 wt% of Capsules D, E, and F (respectively), and 500 ppm of calcium stearate (matrix stabilizer), which were processed via mixing chamber using rolling-rotors, with a rotor speed of 100 rpm, set temperature of 180°C, and a mixing time of 2 minutes. After compression molding ( ⁇ 30 seconds, - 1 bar), the polymeric mass was taken directly from the mixing chamber into a thin plate (1mm).
- Example 9 was formulated with 50 wt% of EVA HM728, -49.5 wt% of HDPE HD7000C, 1.0 wt% of Capsule E, and 500 ppm of calcium stearate (matrix stabilizer), was processed via mixing chamber using rolling-rotors, with a rotor speed of 100 rpm, set temperature of 180°C, and a mixing time of 2 minutes. After compression molding (- 30 seconds, - 1 bar), the polymeric mass was taken directly from the mixing chamber into a thin plate (1mm).
- Example 10 Formulation and processing of the materials - Bottle
- Example 10 was formulated with 49 wt% of EVA VA4018R, 49 wt% of HDPE BS002W, and 2.0 wt% of Capsules G, which was processed in a twin screw extruder, using a screw speed of 350 rpm, throughput rate of 3 kg/h, and a die with one hole.
- the heating zones were set to the following temperatures: 120, 170, 190, 200, 210, 210, 210°C (melt temperature was around 226°C), and the pH of the cooling water bath was maintained around 10.
- the material was pelletized, and then processed via EBM, with a screw speed of 20 rpm, a temperature profile ending in 190°C, mold temperature of 15°C, blow pressure and support air of 2 bar, cooling and blow time of 9 seconds and a total cycle time of 13,5 seconds, where bottles with 25.5 grams and wall thickness of approximately 0.7 mm were produced.
- Example 11 Formulation and processing of the materials- 3D Printed Bottle [00222]
- Example 11 was formulated with 30 wt% of EVA HM2528, -69.5 wt% of HDPE SHC7260 (Green polyethylene), 0.5 wt% of Capsules B, and 300 ppm of zinc stearate (matrix stabilizer), which was processed in a twin screw extruder, using a screw speed of 220 rpm, throughput rate of 4 kg/h, and a die with two holes.
- the heating zones were set to the following temperatures: 60, 120, 135, 150, 160, 160, 160°C (melt temperature was 169°C), and the pH of the cooling water bath was maintained around 8.
- the material was pelletized, re-extruded using a single screw extrusion (melt temperature - 180°C, through a die with one hole), in order to obtain a filament to produce a bottle via 3D Printing (FDM (Fused deposition modeling), with a 3D Printer LeapFrog - Bolt Pro.
- FDM fused deposition modeling
- 3D Printer LeapFrog - Bolt Pro The processing conditions of the 3D printing are provided in Table 11 below.
- Example 12 Formulation and processing of the materials - Masterbatch
- Example 12 was formulated to be a masterbatch formulation with 90 wt% of EVA HM2528, 10 wt% of Capsule B compact with mineral oil (25% oil in the mix), which was processed in a twin screw extruder, using a screw speed of 200 rpm, throughput rate of 2 kg/h, a die with one hole, the heating zones with the following temperatures 80, 110, 125, 140, 150, 150, 150°C (where the melt temperature was 160°C), and the pH of the cooling water bath (in which the strand passed through) was maintained around 10. [00225] Example 13 - Formulation and processing of the materials - Dilution
- Example 13 was formulated with 90 wt% of EVA HM728, 10 wt% of the Masterbatch formulation of Example 12.
- the formulation was processed in a twin screw extruder, using a screw speed of 250 rpm, throughput rate of 3 kg/h, a die with one hole, the heating zones with the following temperatures 80, 110, 125, 140, 150, 150, 150°C (where the melt temperature was 160°C), and the pH of the cooling water bath (in which the strand passed through) was maintained around 10.
- Examples 14, 16, 18, and 20 were formulated with 90 wt% of HD7000C (Ex.14) or FLEXUS 9200 (Ex.16) or BC818 (Ex. 18) or HSC7260 green (Ex.20), 10 wt% of the Masterbatch formulation (Ex. 12).
- the formulations were processed in a twin screw extruder, using a screw speed of 250 rpm, throughput rate of 3 kg/h, a die with one hole, the heating zones with the following temperatures 80, 135, 150, 160, 170, 170, 170°C (where the melt temperature was 180°C), and the pH of the cooling water bath (in which the strand passed through) was maintained around 10.
- HM728 is an EVA grade used in adhesives and expanded plates
- HD7000C is a PE grade used in blow molding
- FLEXUS 9200 is a PE grade used in films
- BC818 is a PE grade used in injection molding and films
- HSC7260 is a biobased PE grade used in injection molding
- CP939 is a PP grade used in injection molding.
- Examples 15, 17, 19, and 21 were formulated with 50 wt% of HD7000C (Ex.15) or FLEXUS 9200 (Ex.17) or BC818 (Ex. 19) or HSC7260 green (Ex.21), 10 wt% of the Masterbatch (Ex. 12), and 40 wt% of EVA HM728.
- the formulations were processed in a twin screw extruder, using a screw speed of 250 rpm, throughput rate of 3 kg/h, a die with one hole, the heating zones with the following temperatures 80, 135, 150, 160, 170, 170, 170°C (where the melt temperature was 180°C), and the pH of the cooling water bath (in which the strand passed through) was maintained around 10.
- Example 22 Formulation and processing of the materials - Dilution
- Example 22 was formulated with 90 wt% of ICP CP393 and 10 wt% of the Masterbatch (Ex. 12), which was processed in a twin screw extruder, using a screw speed of 250 rpm, throughput rate of 3 kg/h, a die with one hole, the heating zones with the following temperatures 100, 180, 180, 180, 190, 190, 190°C (where the melt temperature was 200°C), and the pH of the cooling water bath (in which the strand passed through) was maintained around 10.
- Example 23 Formulation and processing of the materials - Dilution
- Example 23 was formulated with 50 wt% of ICP CP393, 10 wt% of the Masterbatch (Ex. 12), 40 wt% of EVA HM728, which was processed in a twin screw extruder, using a screw speed of 250 rpm, throughput rate of 3 kg/h, a die with one hole, the heating zones with the following temperatures 100, 180, 180, 180, 190, 190, 190°C (where the melt temperature was 200°C), and the pH of the cooling water bath (in which the strand passed through) was maintained around 10.
- a color change may alert a consumer or bystander as to a change in one or more applications including but not limited to food packaging.
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BR112022012138A BR112022012138A2 (en) | 2019-12-19 | 2020-01-08 | ENCAPSULATED INDICATOR, INTELLIGENT POLYMER COMPOSITION, PACKAGING MATERIAL, METHODS FOR FORMING ENCAPSULATED INDICATOR AND FOR FORMING AN INTELLIGENT POLYMER COMPOSITION, AND, PRINTED ARTICLE |
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Publication number | Priority date | Publication date | Assignee | Title |
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BR102012025160A2 (en) | 2012-10-02 | 2013-11-05 | Braskem Sa | ELASTERIC COMPOSITION NOT EXPANDED ON THE BASIS OF ETHYLENE POLYMER AND VINYL ACETATE AND USE OF THE SAME FOR FOOTWEAR |
US9039953B2 (en) | 2011-08-04 | 2015-05-26 | Arburg Gmbh + Co. Kg | Method for producing a three-dimensional object |
US9063111B2 (en) | 2008-06-30 | 2015-06-23 | Braskem S.A. | Hybrid chemical sensor, and, sensitive polymeric composition |
WO2016046216A1 (en) * | 2014-09-23 | 2016-03-31 | Philips Lighting Holding B.V. | Encapsulated materials in porous particles |
WO2018045443A1 (en) * | 2016-09-12 | 2018-03-15 | Braskem S.A. | Intelligent polymer compositions |
US20190315949A1 (en) | 2018-04-16 | 2019-10-17 | Braskem S.A. | Bio-based elastomeric eva compositions and articles and methods thereof |
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CA2268477C (en) * | 1997-07-16 | 2009-02-17 | The Government Of The United States Of America | Food quality indicator device |
US9289528B2 (en) * | 2013-06-26 | 2016-03-22 | Eastman Kodak Company | Methods for using indicator compositions |
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2019
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Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US9063111B2 (en) | 2008-06-30 | 2015-06-23 | Braskem S.A. | Hybrid chemical sensor, and, sensitive polymeric composition |
US9039953B2 (en) | 2011-08-04 | 2015-05-26 | Arburg Gmbh + Co. Kg | Method for producing a three-dimensional object |
BR102012025160A2 (en) | 2012-10-02 | 2013-11-05 | Braskem Sa | ELASTERIC COMPOSITION NOT EXPANDED ON THE BASIS OF ETHYLENE POLYMER AND VINYL ACETATE AND USE OF THE SAME FOR FOOTWEAR |
WO2016046216A1 (en) * | 2014-09-23 | 2016-03-31 | Philips Lighting Holding B.V. | Encapsulated materials in porous particles |
WO2018045443A1 (en) * | 2016-09-12 | 2018-03-15 | Braskem S.A. | Intelligent polymer compositions |
US20190315949A1 (en) | 2018-04-16 | 2019-10-17 | Braskem S.A. | Bio-based elastomeric eva compositions and articles and methods thereof |
Non-Patent Citations (3)
Title |
---|
A. FIDALGOR. CIRIMINNAL. M. ILHARCOM. PAGLIARO, CHEM. MATER., vol. 17, 2005, pages 66 - 86 |
FRANCIS, F.J.: "Colorimetry of food", 1983, WESTPORT: AVI PUBLISHING, article "Physical Properties of Foods", pages: 105 - 123 |
LOWELL, S. ET AL.: "Pore Size and Density", 2004, KLUWER ACADEMIC PUBLISHERS, article "Characterization of Porous Solids and Powders: Surface Area" |
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